14-Electron Rh and Ir silylphosphine complexes and their catalytic activity in alkene functionalization with hydrosilanes

Abstract

Herein we report an experimental and computational study of a family of four coordinated 14-electron complexes of Rh(III) devoid of agostic interactions. The complexes [X–Rh(κ³(P,Si,Si)PhP(o-C₆H₄CH₂SiⁱPr₂)₂], where X = Cl (Rh-1), Br (Rh-2), I (Rh-3), OTf (Rh-4), Cl·GaCl₃ (Rh-5); derive from a bis(silyl)-o-tolylphosphine with isopropyl substituents on the Si atoms. All five complexes display a sawhorse geometry around Rh and exhibit similar spectroscopic and structural properties. The catalytic activity of these complexes and [Cl–Ir(κ³(P,Si,Si)PhP(o-C₆H₄CH₂SiⁱPr₂)₂], Ir-1, in styrene and aliphatic alkene functionalizations with hydrosilanes is disclosed. We show that Rh-1 catalyzes effectively the dehydrogenative silylation of styrene with Et₃SiH in toluene while it leads to hydrosilylation products in acetonitrile. Rh-1 is an excellent catalyst in the sequential isomerization/hydrosilylation of terminal and remote aliphatic alkenes with Et₃SiH including hexene isomers, leading efficiently and selectively to the terminal anti-Markonikov hydrosilylation product in all cases. With aliphatic alkenes, no hydrogenation products are observed. Conversely, catalysis of the same hexene isomers by Ir-1 renders allyl silanes, the tandem isomerization/dehydrogenative silylation products. A mechanistic proposal is made to explain the catalysis with these M(III) complexes.